CN101760227A - Catalytic conversion method for preparing propylene and high octane gasoline - Google Patents
Catalytic conversion method for preparing propylene and high octane gasoline Download PDFInfo
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- CN101760227A CN101760227A CN200810246522A CN200810246522A CN101760227A CN 101760227 A CN101760227 A CN 101760227A CN 200810246522 A CN200810246522 A CN 200810246522A CN 200810246522 A CN200810246522 A CN 200810246522A CN 101760227 A CN101760227 A CN 101760227A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalytic conversion method for preparing propylene and high octane gasoline. Raw oil of different cracking properties enters different reaction regions of a first riser reactor to contact with catalytic cracking catalysts for carrying out cracking reactions so as to separate a spent catalysts from reaction oil gas; the reaction oil gas is separated for obtaining a product comprising the propylene, gasoline and a re-cracking raw material, wherein the re-cracking raw material is transmitted into a second riser reactor to contact with hot regenerated catalysts for carrying out catalytic conversion; and after the spent catalysts in the two riser reactors are burned in a same regenerator, the spent catalysts are respectively returned to the two riser reactors. In the method, the yields of the propylene and the gasoline are obviously increased; the octane value of the gasoline is also obviously improved. Under the condition of largely increasing the yield of the propylene, the yield of dry gas is obviously reduced by more than 80% by weight.
Description
Technical field
The invention belongs to the catalysis conversion method of hydro carbons under the situation that does not have hydrogen, more particularly, is a kind of method that heavy feed stock is converted into propylene and stop bracket gasoline.
Background technology
Propylene is important Organic Chemicals, is the synthon of products such as polypropylene, vinyl cyanide.Along with increasing rapidly of derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in propylene market, the world is 1,520 ten thousand tons of 5,120 ten thousand tons of being increased to 2000 before 20 years, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.
The method of producing propylene mainly is steam cracking and catalytic cracking (FCC), wherein steam cracking is that raw material is produced ethene, propylene by thermo-cracking with lightweight oils such as petroleum naphthas, but the productive rate of propylene only is that FCC is a raw material with decompressed wax oil mink cell focuses such as (VGO) then about 15 heavy %.At present, 66% propylene is produced the byproduct of ethene from steam cracking in the world, and 32% produces the byproduct of vapour, diesel oil from refinery FCC, and a small amount of (about 2%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.
If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face the shortage of lightweight material oil, inefficiency of production and cost and cross high several big restraining factors.
FCC is owing to advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of the propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.
US4,980,053 disclose a kind of hydrocarbon conversion processes of producing low-carbon alkene, and raw material is petroleum fractions, residual oil or the crude oil of different boiling ranges, uses solid acid catalyst in fluidized-bed or moving-burden bed reactor, temperature 500-650 ℃, pressure 1.5-3 * 10
5Pa, weight hourly space velocity 0.2-2.0h
-1, agent-oil ratio 2-12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle behind coke burning regeneration uses.The overall yield of this method propylene and butylene can reach about 40%, and wherein productivity of propylene is up to 26.34%.
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, and this method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, is the catalyzer of matrix with a large amount of inert substances, is raw material with VGO, and the productive rate of propylene also is no more than 20 heavy %.
US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of this method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, this method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into a plurality of reaction zones carries out cracking reaction, with voluminous low-molecular olefine.
Along with Chinese economic development, China's gasoline car recoverable amount increases year by year, and therefore the demand to premium-type gasoline improves day by day.China's motor spirit is mainly from catalytic cracking unit, catalytically cracked gasoline last running part octane value is on the low side, thereby influence the octane value of gasoline, in addition, catalytic cracking diesel oil is second-rate, but catalytic cracking diesel oil contains more mononuclear aromatics, and the mononuclear aromatics in the diesel oil is converted into the increase that gasoline component had both helped gasoline yield, can improve the octane value of gasoline simultaneously again.
Above-mentioned prior art still exists not enough to alkane molecule cracking reaction design, simultaneously, the product of prior art distributes and is that routinely FCC fractionating system is cut, and arene underwater content in gasoline or the diesel oil and low-carbon alkene potential content are underused, and cause the productive rate of propylene and aromatic hydrocarbons on the low side.In order to satisfy the demand of industrial chemicals such as growing propylene, ethene and aromatic hydrocarbons, be necessary to develop a kind of catalysis conversion method that heavy feed stock is converted into a large amount of propylene, ethene and aromatic hydrocarbons.
Summary of the invention
Technical problem to be solved by this invention provides a kind of catalysis conversion method heavy feed stock is converted into propylene and stop bracket gasoline.
Technical scheme of the present invention is a kind of catalysis conversion method of producing propylene and stop bracket gasoline, and this method comprises the following steps:
(1) difficult cracked stock oil enters first riser reactor bottom, contacts with hot regenerated catalytic cracking catalyst, at 600 ℃-750 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(2) reaction effluent separates without finish, mixes with easy cracked stock oil, and easily cracked stock oil is at 500 ℃-670 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-30, the weight ratio of water vapor and raw material is to react under the condition of 0.05-1.0;
(3) reaction effluent separates without finish, and with optional difficult cracked stock oil, easily one or more in cracking stock oil, the cold shock medium mix, stock oil is at 450 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(4) separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst enters revivifier behind stripping, returns first riser tube behind coke burning regeneration, and reaction oil gas goes separation system;
(5) the described reaction oil gas of step (4) enters separation system and separates that to obtain comprising propylene, C 4 olefin, gasoline, boiling range be 180 ℃～250 ℃ the cut and the product of catalytic wax oil;
(6) the described catalytic wax oil of step (5) or/and the aromatic hydrocarbons extracting is handled, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment;
(7) the described C 4 olefin of step (5), the described boiling range of step (5) be a kind of during 180 ℃～250 ℃ cut, the described hydrogenation catalyst wax oil of step (6), the described catalytic wax oil of step (6) raffinated oil or wherein more than one mixture send in second riser reactor as cracking stock again, contact 500 ℃-750 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, wherein reclaimable catalyst is through returning second riser reactor behind the coke burning regeneration in revivifier behind the stripping, and the separation of reaction oil gas is identical with step (5).
Described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, and wherein petroleum hydrocarbon is selected from decompressed wax oil (VGO), normal pressure wax oil (AGO), wax tailings (CGO), deasphalted oil (DAO), vacuum residuum (VR), long residuum (AR), catalytic wax oil and raffinates oil.Other mineral oil is liquefied coal coil, tar sand oil, shale oil.Preferred raw material is selected from that decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil, vacuum residuum, long residuum, heavy aromatics raffinate oil a kind of or more than one mixture wherein.Wherein VGO, AGO, CGO, DAO, VR, AR are the full cut or the part cut of not hydrogenation, or are full cut or part cut behind the hydrogenation.
Described difficult cracking stock is the low-carbon (LC) molecule, is selected from carbonatoms and is a kind of of 2～8 hydro carbons, slurry oil, diesel oil, gasoline or more than one mixture wherein.Described difficult cracking stock both can install from this, also can be from outer device.
Described gasoline is selected from a kind of in present method gained catalytic cracking gasoline, catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, the hydrogenated gasoline or more than one mixture wherein, and wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from the outer gasoline of this device.
Described diesel oil is to be selected from a kind of in present method gained catalytic pyrolysis diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, the hydrogenated diesel oil or more than one mixture wherein, and wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.
Carbonatoms is that 2～8 hydrocarbon can be from catalytic cracking method of the present invention, also can be from technologies such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.
Described cold shock medium is one or more the mixture of arbitrary proportion that is selected from refrigerative regenerated catalyst, refrigerative half regenerated catalyst, reclaimable catalyst and the live catalyst, and wherein refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively.
Described cracking stock again is that C 4 olefin, boiling range are a kind of during 180 ℃～250 ℃ cut, hydrogenation catalyst wax oil, catalytic wax oil raffinated oil or more than one mixture wherein, and wherein each raw material can be from this device and the outer raw material of this device.
Fractionation plant can be the fractionation plant of each reactor catalytic cracking unit separately, also can be the fractionation plant of two shared cover catalytic cracking unit of reactor, can also be independent fractionation plant.
The method of separation of propylene is identical with the method that those of ordinary skills know from reaction oil gas.
Described 180～250 ℃ cut is between the FCC of routine gasoline last running and diesel oil lighting end, its separation method is different from the separation method of existing FCC separation column, its separation method is seen patent of invention 200710120105.0, after separating unit separates, return first riser tube or/and the cracking again of second riser tube.
The boiling range of described catalytic wax oil is preferably greater than 260 ℃ greater than 250 ℃.Catalytic wax oil or/and the aromatic hydrocarbons extracting is handled, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment, returns first riser tube or/and the cracking again of second riser tube.
The catalytic wax oil hydrotreatment is under there is situation in hydrogen, contacts with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under to carry out hydrotreatment resultant.The hydrogenation catalyst wax oil is as the stock oil of cat-cracker.
The heavy aromatics extraction solvent is selected from methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1, the mixture of one or more in the materials such as 2-propylene glycol.The extractive process solvent recovery cycle is used.Extraction temperature is 40～120 ℃, and the volume ratio between solvent and the raw material is 0.5～5.0.Extract is one of a purpose product heavy aromatics, and it is non-aromatics as one of raw material of catalytic pyrolysis that catalytic wax oil is raffinated oil.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for total catalyst weight respectively: the heavy % of zeolite 10 heavy %-50, the heavy % of inorganic oxide 5 heavy %-90, the heavy % of clay 0 heavy %-70.
Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, and the heavy % of preferred 70 heavy %-100, large pore zeolite account for the heavy % of 0 heavy %-50 of zeolite gross weight, the heavy % of preferred 0 heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y constitute.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Clay is selected from kaolin and/or halloysite as matrix (being carrier).
Catalytic cracking catalyst in each reactor is identical, the shared same revivifier regeneration of reclaimable catalyst.
In order to increase the agent-oil ratio of reaction catchment, improve the lytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.Refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7; The reclaimable catalyst carbon content is more than the 0.9 heavy %, and preferably carbon content is the heavy % in 0.9 heavy %～1.2.
Two riser reactors of the present invention can be identical, also can be different.Riser tube can be conventional isodiametric riser tube, also can be the riser tube of various forms reducing.The present invention preferably carries out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.Second riser tube can have a reaction zone, also plural reaction zone can be arranged, preferred two reaction zones.
This technical scheme organically combines technologies such as catalytic pyrolysis and catalytic wax oil hydrogenation, heavy aromatic solvent extracting, produces low-carbon alkene especially propylene and stop bracket gasoline to greatest extent from the lower heavy feed stock of hydrogen richness.The optimum combination that this technical scheme provides different catalytic pyrolysis raw materials and dissimilar catalyzer to carry out cracking reaction.
The present invention compared with prior art has following unforeseeable technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably, for paraffinic base VGO, and productivity of propylene nearly 30 heavy %;
2, gasoline yield increases significantly, and gasoline octane rating improves significantly;
3, under the situation that productivity of propylene increases considerably, dry gas yied reduces significantly, can reduce to reach more than the 80 heavy %.
Description of drawings
Fig. 1 is the method flow synoptic diagram of one of embodiment.
Fig. 2 is two a method flow synoptic diagram of embodiment.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is the method flow synoptic diagram of one of embodiment.
Its technical process is as follows:
The pre-steam that promotes is entered by riser reactor 2 bottoms through pipeline 1, mix with regenerated catalyst from pipeline 7, in the accelerated motion that makes progress of the castering action lower edge of steam riser tube, simultaneously difficult cracking stock oil through pipeline 3 with atomizing steam injecting lift pipe from pipeline 4, mix with the existing logistics of riser reactor, cracking reaction takes place in difficult cracking stock on the hot catalyzer that contains a small amount of charcoal, and upwards accelerated motion.Easily cracking stock oil through pipeline 5 with atomizing steam injecting lift pipe (cracking stock can mix with difficult cracking stock through pipeline line 3 injecting lift pipes again) from pipeline 6, mix with the existing logistics of riser reactor, cracking reaction takes place on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 9, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 22, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 11 in the settling vessel, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 18 through standpipe 8, and main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine.Catalyzer after the regeneration enters riser tube through inclined tube 7.Oil gas in the collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
The pre-steam that promotes is entered by riser reactor 12 bottoms through pipeline 11, mix with regenerated catalyst from pipeline 17, regenerated catalyst is along the riser tube accelerated motion that makes progress under the castering action of steam, simultaneously partly or entirely again cracking stock oil through pipeline 13 with atomizing steam injecting lift pipe from pipeline 14, mix with the existing logistics of riser reactor, cracking reaction takes place in cracking stock on the hot catalyzer that contains a small amount of charcoal again, and upwards accelerated motion.The part again cracking stock oil (as 180～250 ℃ cut) through pipeline 15 with atomizing steam injecting lift pipe 12 from pipeline 16, mix with the existing logistics of riser reactor, this part again cracking stock cracking reaction takes place on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 19, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 22, and catalyst fines returns settling vessel 10 by dipleg.Reclaimable catalyst flows to stripping stage 11 in the settling vessel, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 18 through standpipe 8, and main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine.Catalyzer after the regeneration enters riser tube 2 and riser tube 12 respectively through pipeline 7 and pipeline 17.Oil gas in the collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Mixed oil and gas obtains splitting gas (consisting of hydrogen, C1-C2 alkane and ethene) through separation system 24 separation and goes out device through pipeline 33; Propylene goes out device as one of purpose product through pipeline 32; Propane that separation obtains and butane are drawn through pipeline 34 and are turned back to first reactor; C4 alkene returns riser tube 12 bottoms through pipeline 31,13 successively; Another kind of purpose product stop bracket gasoline goes out device through pipeline 29; Choose wantonly, part light gasoline fraction (forming the various hydro carbons of C5-C8) returns riser tube; 180～250 ℃ cut is all or part of to return riser tube 12 bottoms through pipeline 26; Catalytic wax oil (greater than 250 ℃ cut) enters aromatic extraction unit 27 through pipeline 25, and catalytic wax oil is raffinated oil and returned riser tube 2 middle parts through pipeline 28,5 successively, and the aromatic hydrocarbons that extracting goes out goes out device through pipeline 30.
Fig. 2 is two a method flow synoptic diagram of embodiment.
Its technical process is as follows:
The pre-steam that promotes is entered by riser reactor 2 bottoms through pipeline 1, mix with regenerated catalyst from pipeline 7, in the accelerated motion that makes progress of the castering action lower edge of steam riser tube, simultaneously difficult cracking stock oil through pipeline 3 with atomizing steam injecting lift pipe from pipeline 4, mix with the existing logistics of riser reactor, cracking reaction takes place in difficult cracking stock on the hot catalyzer that contains a small amount of charcoal, and upwards accelerated motion.Easily cracking stock oil through pipeline 5 with atomizing steam injecting lift pipe (cracking stock can mix with easy cracking stock through pipeline line 3 injecting lift pipes again) from pipeline 6, mix with the existing logistics of riser reactor, cracking reaction takes place on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 9, the realization reclaimable catalyst separates with oil gas, oil gas enters collection chamber 22, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 11 in the settling vessel, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 18 through standpipe 8, and main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine.Catalyzer after the regeneration enters riser tube through inclined tube 7.Oil gas in the collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
The pre-steam that promotes is entered by riser reactor 12 bottoms through pipeline 11, mix with regenerated catalyst from pipeline 17, regenerated catalyst is along the riser tube accelerated motion that makes progress under the castering action of steam, simultaneously partly or entirely again cracking stock oil through pipeline 13 with atomizing steam injecting lift pipe from pipeline 14, mix with the existing logistics of riser reactor, cracking reaction takes place in cracking stock (as the hydrogenation catalyst wax oil) on the hot catalyzer that contains a small amount of charcoal again, and upwards accelerated motion.The part again cracking stock oil through pipeline 15 with atomizing steam injecting lift pipe from pipeline 16, mix with the existing logistics of riser reactor, cracking reaction takes place in this part difficult cracking stock on the lower catalyzer that contains certain charcoal, and upwards accelerated motion, the oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 19, the realization reclaimable catalyst separates with oil gas, and oil gas enters collection chamber 22, and catalyst fines returns settling vessel 10 by dipleg.Reclaimable catalyst flows to stripping stage 11 in the settling vessel, contacts with steam from pipeline 21.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 22 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 18 through standpipe 8, and main air enters revivifier through pipeline 20, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine.Catalyzer after the regeneration enters riser tube 2 and riser tube 12 respectively through pipeline 7 and pipeline 17.Oil gas in the collection chamber 22 enters follow-up separation system 24 through main oil gas piping 23.
Mixed oil and gas obtains dry gas (consisting of hydrogen, C1-C2 alkane and ethene) through separation system 24 separation and goes out device through pipeline 33; Propylene goes out device as one of purpose product through pipeline 32; Propane that separation obtains and butane are drawn through pipeline 34 and are turned back to first reactor; C4 alkene returns riser tube 12 bottoms through pipeline 31,13 successively; Another kind of purpose product stop bracket gasoline goes out device through pipeline 29; Choose wantonly, part light gasoline fraction (forming the various hydro carbons of C5-C8) returns riser tube; 180～250 ℃ cut is all or part of to return riser tube 12 bottoms through pipeline 26,13 successively; Catalytic wax oil (greater than 250 ℃ cut) enters hydrotreater 27 through pipeline 25, and the hydrogenation catalyst wax oil returns riser tube 12 middle parts through pipeline 28,15 successively.
The following examples will give further instruction to present method, but therefore not limit present method.
Used raw material is AR among the embodiment, and its character is as shown in table 1.Used extraction solvent is a tetramethylene sulfone among the embodiment.
Catalytic cracking catalyst preparation method used among the embodiment is summarized as follows:
1), with 20gNH
4Cl is dissolved in the 1000g water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP-1 zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 4.0gH
3PO
4(concentration 85%) and 4.5gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; Then handle at 550 ℃ of roasting temperatures and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2), use 250kg decationized Y sieve water with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) again, its PH is transferred to 2-4 with hydrochloric acid, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 2-4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical company catalyst plant product, Al
2O
3Content is 21.7m%), stirred 40 minutes, obtain mixed serum.
3), the MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical company catalyst plant Industrial products of the phosphorous and iron that step 1) is prepared, lattice constant is 2.445-2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+, being drying to obtain the catalytic cracking catalyst sample, consist of 15 heavy % MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Embodiment 1
Method provided by the invention is adopted in the present embodiment explanation, difficult cracking and easy cracking stock enter first reactor, cracking stock enters second reactor again, catalytic wax oil into second reactor of raffinating oil, two reactive systems use same fractionating system catalyzed conversion to generate the situation of propylene and stop bracket gasoline.
This embodiment tests on the middle-scale device of riser reactor according to the flow process of Fig. 1, and directly as easy cracked raw material, propane and butane are as difficult cracked raw material for stock oil A, and the character of stock oil A is listed in table 1, and operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to 27.74 heavy %, and gasoline yield is up to 35.64 heavy %, and RON is up to 97.5, and MON is up to being 85.3.
Method provided by the invention is adopted in the present embodiment explanation, difficult cracking and easy cracking stock enter first reactor, cracking stock enters second reactor again, the hydrogenation catalyst wax oil advances second reactor, and two reactive systems use same fractionating system catalyzed conversion to generate the situation of propylene and stop bracket gasoline.
This embodiment tests on the middle-scale device of riser reactor according to the flow process of Fig. 2, and directly as easy cracked raw material, propane and butane are as difficult cracked raw material for stock oil A, and the character of stock oil A is listed in table 1, and operational condition and product distribute and list in table 2.
As can be seen from Table 2, productivity of propylene is up to heavy by 28.88%, and gasoline yield is up to heavy by 38.28%, and RON is up to 98.5, and MON is up to being 84.3.
Table 1
| The stock oil numbering | ??A |
| Stock oil character | |
| Density (20 ℃), g/cm 3 | ??0.8934 |
| Sulphur content, ppm | ??5600 |
| Nitrogen content, ppm | ??2800 |
| Aromatic hydrocarbons, m% | ??32.6 |
| ??C，m％ | ??86.23 |
| ??H，m％ | ??12.93 |
| The stock oil numbering | ??A |
| Boiling range (ASTM D-1160), ℃ | |
| ??IBP | ??327 |
| ??10％ | ??363 |
| ??30％ | ??409 |
| ??50％ | ??450 |
| ??70％ | ??482 |
| ??90％ | ??504 |
| ??95％ | ??526 |
| ??EP | ??542 |
Table 2
| Embodiment 1 | |
|
| Operational condition | ||
| The catalytic pyrolysis | ||
| Riser tube | ||
| 2 | ||
| Reaction zone I temperature out, ℃ | ??520 | ??520 |
| Agent-oil ratio, m/m | ??8 | ??8 |
| Weight hourly space velocity, h -1 | ??40 | ??40 |
| Water filling (accounting for raw material), m% | ??10 | ??10 |
| Reaction zone II temperature out, ℃ | ??520 | ??520 |
| Agent-oil ratio, m/m |
| Embodiment 1 | |
|
| Weight hourly space velocity, h -1 | ??20 | ??20 |
| Water filling (accounting for raw material), m% | ??10 | ??10 |
| |
||
| Reaction zone III temperature out, ℃ | ??510 | ??515 |
| Agent-oil ratio, m/m | ??10 | ??10 |
| Weight hourly space velocity, h -1 | ??30 | ??30 |
| Water filling (accounting for raw material), m% | ??15 | ??15 |
| Reaction zone IV outlet ℃ | ??500 | ??505 |
| Agent-oil ratio, m/m | ??10 | ??10 |
| Weight hourly space velocity, h -1 | ||
| Water filling (accounting for raw material), m% | ??10 | ??10 |
| The hydrotreatment unit | ||
| Temperature of reaction, ℃ | ??/ | ??350 |
| The hydrogen dividing potential drop, MPa | ??/ | ??13 |
| Volume space velocity, h -1 | ??/ | ??1.5 |
| Hydrogen to oil volume ratio, v/v | ??/ | ??1200 |
| The solvent extraction unit | ||
| Temperature, ℃ | ??100 | ??/ |
| Solvent ratio, v/v | ??3.0 | ??/ |
| Product distributes, m% |
| Embodiment 1 | |
|
| Dry gas | ??4.88 | ??4.96 |
| Liquefied gas | ??47.26 | ??49.60 |
| Propylene | ??27.74 | ??28.88 |
| Gasoline | ??35.64 | ??38.28 |
| Heavy aromatics | ??5.20 | ??/ |
| Coke | ??7.02 | ??6.86 |
| Add up to | ??100 | ??100 |
| Gasoline octane rating | ||
| ?RON | ??97.5 | ??98.5 |
| ?MON | ??85.3 | ??84.3 |
Claims (9)
1. a catalysis conversion method of producing propylene and stop bracket gasoline is characterized in that this method comprises the following steps:
(1) difficult cracked stock oil enters first riser reactor bottom, contacts with hot regenerated catalytic cracking catalyst, at 600 ℃-750 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(2) reaction effluent separates without finish, mixes with easy cracked stock oil, and easily cracked stock oil is at 500 ℃-670 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 2-30, the weight ratio of water vapor and raw material is to react under the condition of 0.05-1.0;
(3) reaction effluent separates without finish, and with optional difficult cracked stock oil, easily one or more in cracking stock oil, the cold shock medium mix, stock oil is at 450 ℃-650 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(4) separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst enters revivifier behind stripping, returns first riser tube behind coke burning regeneration, and reaction oil gas goes separation system;
(5) the described reaction oil gas of step (4) enters separation system and separates that to obtain comprising propylene, C 4 olefin, gasoline, boiling range be 180 ℃～250 ℃ the cut and the product of catalytic wax oil;
(6) the described catalytic wax oil of step (5) or/and the aromatic hydrocarbons extracting is handled, obtains the hydrogenation catalyst wax oil or/and catalytic wax oil is raffinated oil through hydrotreatment;
(7) the described C 4 olefin of step (5), the described boiling range of step (5) be a kind of during 180 ℃～250 ℃ cut, the described hydrogenation catalyst wax oil of step (6), the described catalytic wax oil of step (6) raffinated oil or wherein more than one mixture send in second riser reactor as cracking stock again, contact 300 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 100h with hot regenerated catalyst
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 2-100, the weight ratio of water vapor and raw material is to carry out catalyzed conversion under the condition of 0.05-1.0, reclaimable catalyst separates by cyclonic separator with reaction oil gas, wherein reclaimable catalyst is through returning second riser reactor behind the coke burning regeneration in revivifier behind the stripping, and the separation of reaction oil gas is identical with step (5).
2. according to the method for claim 1, it is characterized in that described easy cracking stock is petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil, vacuum residuum, long residuum, catalytic wax oil and raffinates oil.Other mineral oil is liquefied coal coil, tar sand oil, shale oil.
3. according to the method for claim 1, it is characterized in that described difficult cracking stock is the low-carbon (LC) molecule, be selected from carbonatoms and be a kind of of 2～8 hydro carbons, slurry oil, diesel oil, gasoline or more than one mixture wherein.
4. according to the method for claim 1, it is characterized in that described catalytic converting catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: the heavy % of zeolite 10 heavy %-50, the heavy % of inorganic oxide 5 heavy %-90, the heavy % of clay 0 heavy %-70, its mesolite is as active ingredient, be mesopore zeolite and/or optional large pore zeolite, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from by Rare Earth Y, rare earth hydrogen Y, the super steady Y that different methods obtains, the mixture of one or more in this group zeolite that high silicon Y constitutes.
5. according to the method for claim 1, it is characterized in that described cold shock medium is one or more the mixture of arbitrary proportion that is selected from refrigerative regenerated catalyst, refrigerative half regenerated catalyst, reclaimable catalyst and the live catalyst, wherein refrigerative regenerated catalyst and refrigerative half regenerated catalyst are that reclaimable catalyst obtains through two-stage regeneration and one section regeneration postcooling respectively.
6. according to the method for claim 1, the boiling range that it is characterized in that described catalytic wax oil is greater than 250 ℃.
7. according to the method for claim 1, it is characterized in that described hydrogenation catalyst wax oil, return first riser tube or/and the cracking again of second riser tube or/and catalytic wax oil is raffinated oil.
8. according to the method for claim 1, it is characterized in that described hydrotreatment is under there is situation in hydrogen, contact with hydrotreating catalyst, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h
-1Reaction conditions under carry out hydrotreatment, obtain the hydrogenation catalyst wax oil.
9. according to the method for claim 1, it is characterized in that the extraction solvent that described aromatic hydrocarbons extracting is handled is selected from methyl-sulphoxide, furfural, dimethyl formamide, monoethanolamine, ethylene glycol, 1, the mixture of one or more in the 2-propylene glycol, extraction temperature is 40～120 ℃, and the volume ratio between solvent and the raw material is 0.5～5.0.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2474119A (en) * | 2009-09-28 | 2011-04-06 | China Petroleum & Chemical | A catalytic conversion process for producing more diesel and propylene |
| CN102899078A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN103627426A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Method for improving gasoline yield of catalytic cracking technology and device thereof |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
| CN104560166A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method utilizing petroleum hydrocarbon to produce high-octane gasoline |
| CN104903427A (en) * | 2012-10-19 | 2015-09-09 | 沙特阿拉伯石油公司 | Process for high severity catalytic cracking of crude oil |
| CN113735676A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Method for high-selectivity catalytic cracking of propylene with high yield and gasoline yield increase |
| CN114426854A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of ethylene and BTX |
| CN114605219A (en) * | 2020-12-09 | 2022-06-10 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and gasoline |
| WO2022174435A1 (en) * | 2021-02-22 | 2022-08-25 | 广州智京科技有限公司 | Double settlers – based catalytic cracking device and method |
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| GB2474119A (en) * | 2009-09-28 | 2011-04-06 | China Petroleum & Chemical | A catalytic conversion process for producing more diesel and propylene |
| GB2474119B (en) * | 2009-09-28 | 2013-08-14 | China Petroleum & Chemical | A catalytic conversion process for producing more diesel and propylene |
| US8529754B2 (en) | 2009-09-28 | 2013-09-10 | China Petroleum & Chemical Corporation | Catalytic conversion process for producing more diesel and propylene |
| CN102899078A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN102899078B (en) * | 2011-07-29 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN103627426A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Method for improving gasoline yield of catalytic cracking technology and device thereof |
| CN104903427A (en) * | 2012-10-19 | 2015-09-09 | 沙特阿拉伯石油公司 | Process for high severity catalytic cracking of crude oil |
| CN104903427B (en) * | 2012-10-19 | 2018-01-02 | 沙特阿拉伯石油公司 | The method of high intensity catalytic cracking crude oil |
| CN104560149A (en) * | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method of productive butene |
| CN104560149B (en) * | 2013-10-16 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of hydrocarbons catalytic conversion method of voluminous butylene |
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| CN104560166B (en) * | 2013-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline |
| CN113735676A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Method for high-selectivity catalytic cracking of propylene with high yield and gasoline yield increase |
| CN113735676B (en) * | 2020-05-29 | 2023-10-13 | 中国石油化工股份有限公司 | Method for high-selectivity catalytic pyrolysis of high-yield propylene and high-yield gasoline |
| CN114426854A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of ethylene and BTX |
| CN114605219A (en) * | 2020-12-09 | 2022-06-10 | 中国石油化工股份有限公司 | Method and system for producing low-carbon olefin and gasoline |
| CN114605219B (en) * | 2020-12-09 | 2024-04-02 | 中国石油化工股份有限公司 | Method and system for producing light olefins and gasoline |
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